CH671030A5 - - Google Patents

Description

DESCRIPTION

The invention relates to detergent compositions containing builders, which contain polyethylene terephthalate-poly-oxyethylene terephthalate polymers to accelerate soil release, in particular compositions based on builders and nonionic surfactant, which contain such PET-POET polymers in a stabilized manner, the stabilization taking place by POET polymer melts at elevated temperature with a polyacrylate to form a homogeneous melt and this melt is converted into particle form, the PET-POET polymer and the polyacrylate remaining in intimate contact. The PET-POET polymers so produced are of superior stability, which is demonstrated by the superior properties of accelerated dirt removal during storage, even at elevated temperatures, in contact with alkaline materials such as alkaline detergent builders when these polymers are incorporated into detergent compositions. It was found that this stability is also superior to that of PET-POET polymers which are coated with polyacrylate or intimately mixed with polyacrylate in finely divided form. Incorporating the stabilized, particulate, soil release accelerating polymers into nonionic surfactant detergent compositions will improve the soil and stain removability of these compositions compared to compositions of similar formulations in which the PET-POET polymer and the polyacrylate are mixed Individual powders are present.

The patent literature has described that PET-PO-ET polymers accelerate the soiling of laundry that has previously been treated with such a polymer by washing laundry with a detergent containing the same. Dirt-removing effects are described in U.S. Patent 3,962,152 and British Patent 1,088,984. It has been found that such polymeric materials can be destabilized by anionic surfactants and / or alkaline compounds. Therefore, when making detergent compositions containing PET-POET polymers, these polymers tend to lose their soil release properties when stored when the detergent compositions contain alkaline builder salts such as sodium carbonate or other alkaline materials, with the most significant losses in this activity such compositions occur, which are more alkaline and stored for a long time at higher temperatures. Efforts have therefore been made to stabilize the polymers to accelerate soil release so that they do not lose their desired properties when incorporated into builder-containing detergent compositions.

It has now been found that when a PET-PO-

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ET polymer melts and with a water-soluble polyacrylate such as sodium polyacrylate, preferably with a molecular weight of about 1000 to 5000, e.g. about 2000, in a ratio of about 2: 1 to 8: 1 (PET-POET-Polymers: polyacrylate) and the melt is converted into solid particles 5, in which the polymers mentioned are still in intimate contact, the dirt release properties of the PET-POET polymers are maintained, even if the particles described are stored in contact with particulate alkaline materials such as builder salts for surfactants, which are often present in particulate detergents containing builders. This is surprising, primarily because various other polymeric materials for stabilizing PET-POET polymers are unsatisfactory. Coating powdered 15 PET-POET polymers with a solution of sodium polyacrylate and then drying this coating does not achieve the same desired stabilization, not even by mixing together finely divided powders of these polymeric substances. In order to achieve the results 20 according to the invention, it is necessary to melt the polymers together first. This need is surprising since it would be expected that there would be an interaction between the polymers at elevated temperature or that the elevated temperature would contribute to the destabilization of the polymer accelerating soil removal. As a further desired effect, it has been found that improved cleaning of soiled and stained articles of various types can be achieved by washing them with detergent compositions based on builder and nonionic surfactant which contain the particulate, stabilized, soil release accelerating polymers of the invention. Such washing results in much purer substances than cleaning with detergent compositions which contain PET-POET polymers and sodium polyacrylate in powder form. This result is also surprising since the cleaning effects and the acceleration of the dirt detachment are not related and because the soiled textiles were not previously treated with the substance which accelerates the dirt detachment.

The molecular weight of the PET-POET polymer is usually in the range of about 15,000 to 50,000, preferably about 19,000 to 43,000, particularly preferably about 19,000 to 25,000, e.g. around 22,000. These molecular weights are weight-average molecular weights, in contrast to number-average molecular weights, which are often lower in the case of the polymers according to the invention. In the polymers used, the polyoxyethylene has a molecular weight of about 1000 to 10,000, preferably about 2000 to 5000, particularly preferably 3000 to 4000, e.g. 3400. In these polymers, the molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate units (which are units of the following formula)

O

II

i och2ch2o-c -

o o

II II

-c} and {(0ch2ch2) n-0-c -

O

II

-c}

45

in the range from 2: 1 to 6: 1, preferably 5: 2 to 5: 1, particularly preferably 3: 1 to 4: 1, e.g. at about 3: 1. The ratio 35 of ethylene oxide to the phthalic acid content in the polymer is at least 10: 1, often 20: 1 or more, and is preferably in the range from 20: 1 to 30: 1, particularly preferably 22: 1. It follows that the polymer can essentially be viewed as a modified ethylene oxide polymer in which the phthalic acid part is the smaller component on both a molar and a weight basis. It appears surprising that the polymer with such a low level of ethylene terephthalate or polyethylene terephthalate is sufficiently similar to the polymer of the polyester fiber substrate (or other polymers to which it adheres, such as polyamides) to be washed on, rinsed and dried to be held.

Although the described PET-POET polymer is that which is normally used in accordance with the invention 50 and which is particularly preferred because of its desired effects, other PET-POET polymers as described in the above-mentioned British and US patent can also be used , applied and improved by the method of the invention, ie be stabilized. However, the accelerated dirt removal properties of these materials may be less good than those of the preferred polymers.

The polyacrylate used is a low molecular weight polyacrylate which is usually in the range of about 1000 to 5000, preferably 1000 to 3000 and particularly preferably between 1000 and 2000, e.g. is around 2000. The average molecular weight is usually in the range from 1200 to 2500, for example from 1300 to 1700. Although other water-soluble polyacrylates can sometimes be used instead of the sodium polyacrylate indicated, including some other alkali polyacrylates, e.g. Potassium polyacrylate, it is preferred that such substitutions, if allowed, be limited to a small amount of material, and it is most preferred that the polyacrylate used is an unsubstituted sodium polyacrylate. Such materials are available from AL-CO CHEMICAL CORPORATION under the name Al-cosperse. The sodium polyacrylates are available as clear, amber-colored liquids or powders that are completely soluble in water, the solutions having a solids content of about 25 to 40%, e.g. Have 30% and the pH of such a solution or a 30% aqueous solution of a powder is in the range from 7.5 to 9.5. Of these products, preferred are those currently sold as Alcosperse 104, 107,107 D, 109 and 149, with Alcosperse 107 D (100% solid powder) being particularly preferred, although Alcosperse 107 (a 30% aqueous solution) instead can be used with slight differences in results (provided that it is dried first). Both are sodium polyacrylates, the liquid (107) having a pH in the range from 8.5 to 9.5 and the pH of the powder (107 D) at a concentration of 30% in water in the range of 7 , 0 to 8.0. The powder is preferably anhydrous, but may contain a small amount of water, usually less than 10%, which is largely removed during the melting process.

In order to produce the stabilized, soil release accelerating polymer according to the normal method of the invention, the PET-POET polymer is melted for liquefaction by bringing it to a temperature above its melting point, preferably in the range of 70 to 150 ° C, and then as described with powdered solid sodium polyacrylate. If the melt is uniform, it can be cooled. The solidified mass can be crushed by suitable measures. Mass is preferably used

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assumed the cryogenic grinding or milling or flaking, so that the product is obtained as a finely divided powder or in the form of flakes which are easily miscible with other components of a builder-containing detergent composition and are not appreciably separated from such a composition. The cryogenic comminution, which is often carried out at a temperature below 0 ° C and sometimes below -50 ° C, is carried out by grinding or other comminution in the presence of liquid nitrogen or other cryogenic material. Alternatively, a suitable grinder or grinder, such as a hammer mill, a cage mill, or a Raymond Imp mill, can be used and solid carbon dioxide (dry ice) can be mixed with the resins to be milled, or other cooling devices, instead of liquid nitrogen or other cryogenic cooling liquid be used to prevent the material from overheating and to keep it in a cold, slightly brittle form. Instead of the mentioned shredding devices, other equivalent ones can be used including the Raymond ring mill, which has an internal separator and allows the production of very fine, resin-like materials.

Instead of crushing the PET-POET and polyacrylate melt in the cryogenic or cryogenic grinder, it can be spray-cooled to give beads of desired shape and size that typically pass through a No. 10 sieve (U.S. sieve series) , preferably through a No. 30 sieve.

The product obtained by the methods of the invention can be viewed as a PET-POET polymer that carries polyacrylate. Since the polyacrylate content is relatively low (although its effect is significant), the PET-POET polymer offers a medium with which the polyacrylate can be distributed in any detergent composition with which it is mixed. In addition to the stabilizing effect that the polyacrylate exerts on the PET-POET polymer, the polymer thus contributes to the stretching of the polyacrylate, so that it can be distributed more evenly in the detergent composition and thus more uniformly impart the desired properties of the polyacrylate to this composition , which include accelerating the removal of clay stains from laundry during washing and preventing the re-deposition of dirt on the laundry during washing. The "carrying" of the polyacrylate by the stabilized polymer also eliminates the need to spray the detergent beads or base beads with a polyacrylate solution to evenly distribute them in the detergent.

The primary purpose of the stabilized PET-POET polymers is to accelerate the removal of dirt in detergent compositions. It has been found that laundry, especially those made from polyester or polyester mixtures (usually with cotton) releases light dirt of various types to the washing water when washing with detergents based on builders and surfactants, in particular nonionic surfactants, if the laundry is soiled, after being washed with such a detergent composition containing the PET-POET polymer. Part of the polymer is retained on the laundry during washing so that it is present when the laundry is subsequently soiled and its presence accelerates the removal of the dirt and / or stain during subsequent washing. One might have expected the polyacrylate in the same particles as the PET-POET polymer to accelerate the dispersion of the polymer and prevent it from being deposited on the laundry, but this is not the case. Instead, the polyacrylate increases the activity to accelerate the soil detachment of the PET-POET polymer in detergent compositions by preventing decomposition or degradation of the polymer when it comes into contact with alkaline materials, such as in builder-containing detergent compositions in which the build-up dersalz is alkaline.

The detergent compositions to which the stabilized PET-POET polymers of the invention can be added or in which they can be incorporated to achieve the desired soil release accelerating properties are detergent compositions based on builders and surfactants. The surfactant is normally a non-ionic surfactant, although anionic surfactants are useful in some cases. Anionic surfactants tend to inactivate the PET-POET polymer. However, if they are used in small amounts in detergent compositions which mainly contain nonionic surfactant, the use of the stabilized PET-POET polymers according to the invention leads to detergents with better dirt-accelerating action than if the PET-POET polymer were not without it fused stabilizing polyacrylate is applied.

Of the nonionic surfactants, the condensation products of ethylene oxide and / or propylene oxide are preferably used with one another and with basic substances containing hydroxyl groups, such as higher fatty alcohols, alcohols of the oxotype and nonylphenol. A nonionic surfactant in which the higher fatty alcohol has 10 to 20, preferably 12 to 15 or 16 carbon atoms and which contains about 3 to 20 or 30 ethylene oxide groups per mole, preferably 6 to 11 or 12, is particularly preferred. Most preferred are nonionic surfactants in which the higher fatty alcohol has 12 to 15 or 12 to 14 carbon atoms and which contain 6 or 7 to 11 moles of ethylene oxide. Of these surfactants, Alfonic 1214-60C from the Conoco Division of E.I. DuPont De Nemours, Inc. and the Neodole 23-6.5 and 25-7 from Shell Chemical Co. In addition to their good cleaning properties for oily and greasy dirt deposits on the laundry and their excellent compatibility with the polymers according to the invention, their particularly attractive properties include Soil release is a comparatively low melting point, which is still well above room temperature, so that it can be sprayed onto base beads as a liquid that quickly solidifies after it has penetrated the beads.

Various builders and builder combinations which supplement and improve the washing action of the nonionic surfactants include both water-soluble and water-insoluble builders. Of the water-soluble builders, which are preferably used as a mixture, both inorganic and organic builders can be used. Preferred inorganic builders include various phosphates, usually polyphosphates such as the tri-polyphosphates and pyrophosphates, especially sodium tripolyphosphates and sodium pyrophosphates, e.g. Pentasodium tripolyphosphate, tetrasodium pyrophosphate; Sodium; Sodium bicarbonate and sodium silicate and mixtures thereof. Instead of a mixture of sodium carbonate and sodium bicarbonate, sodium sesquicarbonate can often be used. The sodium silicate used normally has a Na20: SiO2 ratio of 1: 1.6 to 1: 3, preferably 1: 2.0 to 1: 2.4 or 1: 2.8 e.g. 1: 2.4.

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Of the water-soluble inorganic builder salts, the phosphates are mostly used with a lower proportion of sodium silicate, the carbonates with bicarbonate, and sometimes with a lower quantity of sodium silicate, and the silicate is hardly used alone. Instead of using the individual polyphosphates, it is sometimes preferred to use mixtures of sodium pyrophosphate and sodium tri-polyphosphate in ratios of 1:10 to 10: 1, preferably 1: 5 to 5: 1. Of course, there can be changes in the chemical structure of the phosphates during treatment in the crutcher and spray drying, so that in this regard the end product may differ somewhat from the constituents given in the crutcher.

Of the water-soluble organic builders, salts of nitrilotriacetic acid, e.g. Trisodium nitrilotriacetate (NTA), preferably as a monohydrate, is preferred. Other nitrilotriacetates such as disodium nitrilotriacetate are also useful. The various water-soluble builder salts can be used in hydrated forms, which are often preferred.

Other suitable water-soluble builders include the inorganic and organic phosphates, borates, e.g. Borax, citrates, gluconates, ethylenediaminetetraacetates and imino-diacetates. The various builders are preferably in the form of their alkali salts, either as sodium or potassium salts or mixtures thereof, with sodium salts normally being particularly preferred. In some cases, for example, when neutral or weakly acidic detergent compositions are to be prepared, acidic forms of builders, particularly organic builders, may be preferred, but normally the salts are either neutral or basic, usually a 1% aqueous solution of the detergent composition pH in the range of 9 to 11.5, e.g. 9 to 10.5.

Insoluble builders, generally of the zeolite A type, can be used to advantage in the compositions of the invention, with hydrated zeolites X and Y also useful, as well as naturally occurring zeolites and zeolite-like materials or other ion-exchanging insoluble compounds that can serve as builders. Of the various zeolite A products, zeolite 4 A is preferred. These substances are known, processes for their preparation need not be described here. They usually correspond to the formula

(Na20) x • (Al203) y

(Si02) z • w H20

where x is 1, y is 0.8 to 1.2, preferably about 1, z is 1.5 to 3 "5, preferably 2 to 3 or about 2 and w is 0 to 9, preferably 2.5 to 6 .

The zeolite builders are said to be monovalent, cation-exchanging zeolites, i.e. an aluminosilicate with a monovalent cation such as sodium, potassium, lithium (if possible) or other alkali metal or ammonium. Preferably the monovalent cation of the zeolite molecular sieve is an alkali metal cation, especially sodium or potassium and most preferred is sodium. The zeolites, in their crystalline or amorphous form, are capable of reacting quickly enough with calcium ions in hard water so that, alone or together with other water-softening compounds in the detergent composition, they soften the washing water before these ions react adversely with others Components of the detergent composition comes. The zeolites used can be characterized as having a high exchange capacity for calcium ions, which is normally around 200 to 400 or more milligram equivalents of calcium carbonate hardness per g of aluminum silicate, preferably 250 to 350 mg.eq./g on an anhydrous zeolite basis. They also preferably reduce the hardness in wash water quickly, usually within the first 30 seconds to 5 minutes after addition to the wash water, and tsar 5 to a hardness of less than one milligram CaCO3 per liter within this time. The hydrated zeolites normally have a moisture content in the range of 5 to 30%, preferably about 15 to 25%, particularly preferably 17 to 22%. z? 0% If the zeolites are added to a Crutcher mixture from which base beads are made, they should be finely divided and have extreme particle diameters of up to 20 microns, e.g. 0.005 to 20 microns, preferably 0.01 to 8 microns average particle size, e.g. 3 to 7 microns (crystalline) and 15 0.01 to 0.1 microns e.g. 0.01 to 0.05 micron (amorphous). Although the outermost particle sizes are much smaller, the zeolite particles are usually in the range of 100 to 400, preferably 100 to 325 U.S. sieve series when added to the crutcher to make the base beads. In the base beads, the zeolite or zeolites are often desirably accompanied by suitable builder salt (s), such as sodium tripolyphosphate, sodium carbonate, sodium bicarbonate. Sodium silicate has a tendency to agglomerate with zeolites, so that their content in base beads containing zeolite as a builder is limited, for example to 2 or 3%, or they are omitted, particularly in the case of formulations containing carbonate. However, sometimes larger amounts, such as 5 to 10%, may be present, such as in products containing 30 NTA as a builder.

When the preferred nonionic surfactants are used in detergent compositions to which the powder or flakes of the invention 35 are added to improve soil release properties, either polyphosphate or carbonate builders are normally used. However, because of their higher alkalinity, the carbonates have a more disadvantageous effect on the stability of the PET-POET polymer, which is why detergent compositions containing carbonate as a builder, 40 which contain non-stabilized PET-POET polymer, frequently have their activity to accelerate soil detachment after relatively short storage times to lose. For this reason, the greatest need for the present invention is in detergent compositions containing carbonate as Builder 45.

In addition to surfactant and builder, detergent compositions generally also contain a limited amount of moisture and various auxiliaries. Possible auxiliaries are textile softening agents such as bentonite and other clay textile softening agents, fluorescent brighteners such as distilbene whiteners, enzymes such as proteolytic and amylolytic enzymes, coloring substances such as dyes and pigments and perfumes.

In the preferred detergents, the nonionic surfactant (preferably Neodol 23-6.5) is subsequently sprayed onto base beads (mainly builders) and makes up 10 to 30%), preferably 15 to 25 and particularly preferably about 20% of the final composition. In the final composition the moisture content is usually 4 to 60 14, preferably 5 to tO, e.g. approximately ? or 8%, the level of fabric softening clay is usually 1 to 5, preferably 2 to 4, e.g. 3%, the enzyme content is normally 0.5 to 3, preferably 1 to 2, e.g. 1.5%, the polyacrylate content 0.3 to 3, preferably 0.5 to 2, e.g. 1 or et-65 wa 1% and the content of PET-POET polymer 2 to 10, preferably 2 to 6, and particularly preferably about 4%. Such compositions can often contain a relatively small amount, usually 0.5 to 3%, of magnesium sulfate

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included, which is added to the crutch mixture in order to prevent undesired settling of the crutch mixture to produce the base beads. In order to produce the detergent compositions described, a crutcher mixture is prepared at a temperature of about 50 to 70 ° C. and with a moisture content of about 30 to 60% of clays, builders, magnesium sulfate, coloring substances and fluorescent brighteners and spray-dried in the usual way, a Conventional spray tower is used in which hot combustion gases dry atomized droplets of the Crutcher mixture to the base spheres, which typically have particle sizes in the range of 10 to 100 U.S. sieve series. Molten nonionic surfactant, which is absorbed and solidified in the beads, is sprayed or dripped onto such dried particles, after which the powdered or flaky stabilized PET-POET polymer, which has smaller particle sizes than No. 30 US, is mixed with the resulting composition Sieve row (preferably No. 30 to 100). Then powdered enzyme is optionally added. Alternatively, in some processes, the stabilized polymer can be mixed with the powdered enzyme before it is mixed with the rest of the particulate detergent. In some processes, the stabilized polymer can be mixed with the base beads prior to application of the nonionic surfactant, which nonionic surfactant can then serve to hold the polymeric particles more firmly to the base beads. The various mixing processes can be carried out in known inclined drum or twin bowl mixers or in other suitable devices. Any perfume present can be added at any convenient stage, but is usually the last component added.

The following examples are intended to illustrate the invention. In the examples, the description and the claims, unless otherwise stated, all parts and percentages are by weight and all temperatures are in ° C.

example 1

component

percent

Zeolite 4A, hydrate (20% moisture

content, powder)

26.0

Sodium carbonate, anhydrous

18.3

Sodium bicarbonate

15.7

Bentolite L (textile softening clay)

3.0

Fluorescent brightener (stilbene type)

1.7

Proteolytic enzyme (Maxatase MP)

1.5

Magnesium sulfate

1.0

Blue dye

0.1

Neodol 23-6.5

20.0

Alkaril QCF (PET-POET substance for

Acceleration of dirt removal)

4.0

Alcosperse 107D (stabilizer)

1.0

Perfume

0.2

humidity

7.5

100.0

To prepare a detergent composition according to the above approach, an aqueous Crutcher mixture, which contained about 50% water and the formal proportions of zeolite, carbonate, bicarbonate, Bentolite L, fluorescent brightener, magnesium sulfate and dye, was first prepared and at a temperature of about 60 ° C spray dried in a conventional spray drying tower of the type used to spray dry various commercial detergent compositions. The base beads produced had particle sizes in the range of 10 to 100 U.S. sieve series. They were then sprayed with non-ionic surfactant in the liquid state (melted), which had a temperature of about 55 to 60 ° C., in a suitable mixer, such as an inclined rotary drum or a twin-bowl mixer.

Then the powdered enzyme was mixed into the detergent composition, followed by the stabilized (containing sodium polyacrylate) PET-POET polymer. The stabilized polymer had previously been prepared by melting the formal amount of Alkaril QCF (preferably anhydrous, but a small amount of moisture may be present) at a temperature of about 82 ° C and mixing in the formal amount of Alcosperse 107D (sodium polyacrylate). After thoroughly mixing these components together to form a uniform melt, the melt was cooled and solidified. The resulting mass was cryogenically ground using any of the milling devices mentioned above, preferably a hammer or cage mill, to give particles which passed through a No. 30 U.S. sieve series, and preferably sizes in the range of numbers 30 through 100 U.S. sieve rows had. After the stabilized PET-POET polymer, in the particles of which the stabilizing polyacrylate was present, was mixed with the particles of the detergent composition, the formal amount of perfume was sprayed onto the mixture in motion or mixed in one of the devices mentioned above. The product obtained was a satisfactory detergent composition containing builder and nonionic surfactant, good cleaning power and with good dirt-accelerating properties. The soil release accelerating polymer contained therein is stabilized so that the composition shows a significantly greater soil release acceleration after longer storage or two weeks of storage at elevated temperature than a comparative composition of the same approach in which the Alkaril QCF is present in the base beads or alone the particulate detergent composition has been applied (without the presence of polyacrylate).

It is surprising that the soil release accelerating effect of the detergent composition according to the invention of this example after aging is superior to that of a composition of the same formulation (4: 1 PET-POET. "Polyacrylate) in which QCF and alcosperse powder are mixed together and then The compositions according to the invention are also superior to compositions of the approach of this example with regard to the acceleration of dirt detachment, in which powdered QCF is applied to the granular detergent composition and then the formal amount of Alcosperse 107D in aqueous solution (or Alcosperse 107) the detergent particles were sprayed on.

In order to test the anti-soiling effect of the product of the invention against a comparative product containing the same amount of PET-POET polymer, detergent compositions of the above approach were made, one with the stabilized anti-soiling polymer and the other with the same amount of this polymer was added which was not previously subjected to the stabilization treatment according to the invention. The two products were then stored at 43 ° C for 2 weeks, which is close to the higher temperatures that are reached in some warehouses. After this storage, both the «experimental» and the «comparison» product were used to create clean, double-sided polyester patterns in

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Wash water with a hardness of 150 ppm as calcium carbonate (3: 2 calcium: magnesium hardness salt ratio) at a temperature of 49 C in an automatic washing machine, and thereby deposit the polymer that accelerates the dirt detachment, the detergent concentration in the washing water being 0. Was 06%. The soiled test samples were then washed with the same detergent at the same concentration and in the same type of washing water. Then the percentage of dirt removal was measured. It was found that the experimental formulation lost 1.2% of its initial dirt-removing performance (before aging), whereas the product containing the “regular” PET-POET polymer lost 84.5% of its initial dirt-removing ability . Before aging, the dirt-removing ability 15 of both products, experimental and comparative, was essentially the same.

If, instead of melting the polyacrylate with the dirt-accelerating polymer and then cooling and crushing the mass, 20 the powdered PET-POET polymer and powdered polyacrylate were mixed and mixed with the detergent composition to produce a product of the same approach as in mixed in this example, it was found after accelerated aging tests that the polymer accelerating the soil release 25 still decomposed considerably. Similar results were obtained when the unstable polymer was mixed with the detergent composition in the amounts indicated and the formulaic amount of polyacrylate in aqueous solution was sprayed onto the polymer and other ingredients of the detergent composition.

In a test known as the multi-stain test to determine the cleaning power of detergents, various stains including grapefruit juice, blue 35 cake, brewed tea, cranberry juice, beef liver blood, chocolate sugar pudding, potting soil, brandy black tone, liquid make-up, sebum / particle-shaped Dirt, black Bic feather ink, barbeque sauce, red crisco margarine and French Dressing 40 applied to various textiles including Dacron-cotton blend, Qiananylon, cotton and double-faced Dacron, textiles similar to those found in household linen. The stained and soiled textiles were seen in test washing machines. The degrees of reflection (which serve as a measure of the cleaning power) of the various test samples after washing and drying them were determined. When using the non-aged product according to this example of the invention compared to a comparative product without PET-POET polymer and polyacrylate, which, however, was otherwise the same as the formulation of this example, it was found that the total sum of the Rd values for the applied 22 different sample combinations in the experimental was significantly higher 55 than in the comparative product, which is an indication of the improved cleaning power. This is not an indication of the acceleration of dirt detachment, since the samples had not been washed with the detergent composition to deposit the PET-POET polymer prior to soiling.

Example 2

A detergent composition was prepared with the stabilized PET-POET polymer according to the procedure described in Example 1 65, except that the melting of the PET-POET polymer and polyacrylate at a temperature in the range of 130 to 150 ° C

took place. The product produced had the same proportions as in Example 1, but the stabilized polymer had particle sizes that allowed it to pass through a No. 16 sieve (U.S. sieve series) instead of a No. 30 sieve. In this product, the stability of the soil release accelerating substance was tested in the same manner as in Example 1. The loss after 2 weeks of accelerated storage was found to be only 0.6%.

In a variation of this example, the stabilized polymer (in which polyacrylate was present) was applied to the base beads before spraying the nonionic surfactant. The product of this process showed a loss of soil release accelerating activity (or destruction of the PET-POET polymer) of 9.1%. When the PET-POET polymer and sodium polyacrylate were applied to the base beads or detergent beads as a mixed powder (not melted, chilled, and ground beforehand), the loss of soil release activity was much higher, about 30%.

Example 3

component

Pentasodium tripolyphosphate Neodol 25-7 (or Neodol 23-6.5) moisture

Alkaril QCF (PET-POET polymer) sodium polyacrylate (Alcosperse 107D) sodium silicate (Na20: Si02 = 1: 2.4)

Enzyme (Maxatase MP)

Fluorescent brightener (Tinopal 5BM) perfume

Blue dye

Percent 59.4 20.0 9.5 4.0 1.0 3.0 1.5 1.3 0.2 0.1 100.0

A detergent composition according to the above approach was prepared in essentially the same manner as described for Example 1, except that the sodium tripolyphosphate, the fluorescent brightener and dye were mixed with one another in the crutcher and spray-dried to form base beads, the nonionic surfactant onto the obtained Base beads (with particle sizes in the range of numbers 10 to 100 US sieve series) were sprayed, then the powdery enzyme and the stabilized PET-POET polymer (which contained sodium polyacrylate) were mixed with the detergent beads and this mixture was then perfumed.

The product obtained is a satisfactory detergent containing builder and nonionic surfactant, good cleaning power and with useful properties of accelerated dirt removal. The soil release accelerating polymer of the composition is stabilized in such a way that after prolonged storage at room temperature or after two weeks of storage at elevated temperature, the composition shows a stronger soil release accelerating effect than a comparison product of the same composition in which the Alkaril QCF is present in the base beads or applied only to the particles of the detergent composition (in both cases without the presence of polyacrylate). As mentioned in the composition of Example 1, the dirt-accelerating effect of the detergent composition according to the present example after aging is superior to that of a similarly aged composition of the same batch (which also contains PET-POET and polyacrylate in a 4: 1 ratio), in the QCF and Alcosperse 107D powder mixed together without melting and then

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on the detergent pellets, in powder form. The compositions according to the invention are also superior to compositions according to the approach of this example in terms of the dirt release acceleration after aging, in which powdered QCF is added to the detergent beads and the formal amount of Alcosperse 107D in aqueous solution (or Alcosperse 107) is then sprayed onto the detergent particles.

Overall, if the soil release accelerating effect and cleaning power of the composition of the invention are measured as described in Example 1, and if the described comparison products are tested in the manner specified in this example, essentially the same results can be achieved as reported in that example and thus to demonstrate the superiority of the compositions according to the invention, in which previously melted Alkaril QCF-Alcosperse 107D is present, compared to a comparative product. These results are confirmed by repeated washing of soiled laundry with the compositions according to the invention.

Example 4

If the components of the batches of Examples 1 and 3 were varied as indicated in the description and the proportions were changed by ± 10%, ± 20% and ± 30%, each 8

but remained within the predetermined ranges, detergent compositions with improved stability compared to comparative products were obtained, which did not contain the stabilized PET-POET polymers according to the invention.

if the processes for the preparation of the stabilized polymers are modified, as indicated, to improve the stability of the PET-POET polymer and are suitable for use in detergents which contain alkaline builders, it being assumed that the detergents contribute to long storage times or storage times exposed to elevated temperatures.

This gives, for example, proportions of 15 nonionic surfactant, builder, PET-POET, polyacrylate and moisture in the range from 10 to 30%, 30 to 75%, 2 to 10%, 0.3 to 3% and 4 to 14 %, preferably 15 to 25%, 50 to 70%, 2 to 6%, 0.5 to 2% or 5 to 11% superior builder-containing soil release accelerating detergent compositions. If the builder is a mixture of sodium carbonate, sodium bicarbonate and zeolite, the proportions of these components are preferably in the range of 10 to 30%, 10 to 25% and 15 to 40%. When the builder is sodium tripolyphosphate or a mixture thereof with sodium pyrophosphate, the proportion thereof is usually in the range from 30 to 75%, preferably 50 to 70%.

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Claims (14)

671 030 2nd PATENT CLAIMS 1. Detergent composition with accelerated soil release based on builder and nonionic surfactant characterized by a content of a cleaning amount of nonionic surfactant, an amount of alkaline builder having a builder effect, a soil release accelerating amount of a soil release accelerating polymer made of polyethylcentcrephthalate (PET) and polyoxyethylene terephthalate (POET), and a stabilizing amount of a water-soluble polyacrylate (PA) which stabilizes the PET-POET polymer against decomposition and loss of dirt-removing properties when stored in contact with alkaline materials, the PET-POET and PA polymers being solid Particles are in intimate contact and the other components of the detergent composition are in particulate form. 2. Composition according to claim 1, characterized in that the PET-POET polymer has a MW in the range of about 15,000 to 50,000, that the polyoxyethylene of the POET has a MW of about 1000 to 10,000, that the Molar ratio of ethylene terephthalate to POET units is 2: 1 to 6: 1, and that the PA polymer is sodium polyacrylate with a MW of about 1000 to 5000. 3. Composition according to claim 2, characterized in that the PET-POET polymer has a MW of 19,000 to 43,000, the polyoxyethylene thereof has a MW of 2500 to 5000, and that the PA polymer sodium polyacrylate with a MW in is in the range of 1000 to 3000. 4. Composition according to claim 3, characterized in that the nonionic surfactant is a condensation nroHiikt of 3 to 30 ethylene oxide groups per mole of higher fatty alcohol, which has 10 to 20 carbon atoms, and that the builder from the group consisting of zeolites and water-soluble alkaline polyphosphates, Carbonates, bicar bonates, silicates, nitrilotriacetates, borates, citrates, gluconates and mixtures thereof. 5. Composition according to claim 4, characterized by 10 to 30% of a nonionic surfactant, which is the condensation product of a higher fatty alcohol with 12 to 15 carbon atoms and 6 to 12 moles of ethylene oxide, 30 to 75% of a builder or builder mixture, 2 to 10% PET POET polymer with a MW of 19,000 to 25,000, 0.3 to 3% sodium polyacrylate and 4 to 14% moisture. 6. The composition according to claim 5, characterized in that the builder is sodium tripolyphosphate. 7. The composition according to claim 5, characterized in that the builder is a mixture of sodium carbonate, sodium bicarbonate and zeolite. 8. Composition according to claim 5, characterized in that the proportions of these components 15 to 25% nonionic surfactant, 50 to 70% builder, 2 to 6% PET-POET polymer, 0.5 to 2% polyacrylate and 5 to 11% Amount of moisture. 9. The composition according to claim 6, characterized in that it contains 50 to 70% pentasodium tripolyphosphate. 10. The composition according to claim 7, characterized by 10 to 30%, 10 to 25%) or 15 to 40% of the builder components thereof. 11. The composition according to claim 9, characterized by about 20% nonionic surfactant, 60% pentasodium tripolyphosphate, 4% PET-POET polymer, 1% sodium polyacrylate and 10%) moisture. 12. The composition according to claim 10, characterized by about 20% nonionic surfactant, 26% zeolite, 18% sodium carbonate, 16% sodium bicarbonate, 4% PET-POET polymer, 1% sodium polyacrylate and 8% moisture. 13. A process for the commercial washing of laundry and to give it the dirt-removing properties, characterized in that the laundry is washed in water containing a washing and dirt-removing portion of a composition of claim 1. 14. The method according to claim 13, characterized in that the laundry is washed repeatedly with the composition after intermittent soiling of the same.